Milled submicron organic biocides with narrow particle size distribution, and uses thereof

Abstract

A method of milling substantially insoluble solid organic biocides to form a micron or sub-micron product having a narrow particle size distribution is presented. The milling involves wet milling of the organic biocide with high density milling media having a diameter between 0.1 mm and 0.8 mm, preferably between 0.2 mm and 0.7 mm, and a density equal to or greater than 3.8 g / cc, preferably greater than 5.5 g / cc, in a ball mill using between about 40% and 80% loading of the mill volume with milling media, and having the organic biocide suspended in an aqueous milling liquid which comprises one or more surface active agents. The milling speed is preferably high, for example from about 1000 rpm to about 4000 rpm. The milled product can be used in foliar applications at a lower effective dosage than prior art formulations, can be used in improved antifouling paint formulations, and can be used in new applications such as the direct injection of solid organic biocide particulates in wood to act as a long lasting wood preservative.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority to co-pending U.S. patent application Ser. No. 10 / 868,967 filed Jun. 17, 2004, and to U.S. Provisional Application titled: MILLED SUBMICRON CHLOROTHALONIL WITH NARROW PARTICLE SIZE DISTRIBUTION, AND USES THEREOF, filed on Oct. 8, 2004.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] Not applicable INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC [0003] Not applicable SEQUENCE LISTING [0004] Not applicable FIELD OF THE INVENTION [0005] The present invention relates to a method of producing submicron-sized organic biocide particles, methods of packaging same, and uses thereof. More particularly, the invention relates to use of high density milling media having a diameter between 0.1 and 0.8 mm to provide unexpected particle size reduction and narrow particle size distribution even for organic biocides known to be difficult to mill. This milled organic biocidal produc...

AI Technical Summary

Benefits of technology

[0041] When combining a plurality of particulate biocides into a slurry, it is advantageous to make the dispersants and surfactants be compatible one with another. Using anion dispersants on a first biocide and cationic dispersants on the second biocide can result in undesired interactions when the slurry is prepared.

[0043] In some instances the second biocide is present in or as an organic liquid. In such cases, the organic liquid can be solubilized in solvent, emulsified in water, and then added to the first biocide before or during milling, or less preferably after milling. The surface of the first biocide can be made compatible with the organic phase of the emulsion, and the liquid or solvated biocide can coat the primary particles. Advantageously, solvent can be withdrawn, for example by venting the gases above the biocidal composition or by drawing a vacuum. The liquid biocide will subsequently be bound to the surface of the particulate biocide. Not only does this have the advantage of providing the two biocides in close contact so synergy will be observed, but also this provides a method for broadcasting the liquid emulsion without exposing field personnel (if the composition is for foliar applications), painters (if the composition is for non-fouling paints or coatings), and wood preservation personnel from exposure to potentially harmful solvents. Advantageously, the particulate biocidal composition, be it slurry, wettable powder, or granules, can be substantially free of volatile solvents.

Problems solved by technology

The efficient use of organic pesticides is often restricted by their inherent poor water-solubility.

All of these approaches have drawbacks.

Application of a dust is associated with drift, poses a health hazard, and is inefficient.

Solutions and emulsions that require an organic solvent are undesirable, since the solvent serves no other purpose but to act as a carrier for the product.

As such, the solvent adds an unnecessary cost to the formulation and is an added health risk.

Finally, emulsions are generally unstable and must be prepared at point of use, typically in the hours or minutes before use, and minor changes in the formulation, for example by addition of another biocide, may cause the emulsion to break and separate.

Additionally, particle size reduction below certain values (which depend on the product characteristics) can in the past only be achieved through expensive and elaborate procedures, and such procedures quickly price the product out of the market.

It is known to mill chlorothalonil, but no milling process had ever achieved a reduction in the d50 (the volume average diameter) below about 2 microns.

This wide particle size distribution is common, and it severely limits the benefits of the low particle size product, e.g., when used in paints, wood preservatives, and foliar applications.

However, while 57% by weight of particles of copper hydroxide in a particular lot of Champ DP® was 0.2 microns or smaller, when we tried to inject this material into wood this Champ DP® material plugged the surface of the wood and would not penetrate into the wood matrix.

Further, extended grinding times using milling media routinely used in the art 1) will not provide a more uniform product, and 2) will not significantly lower the d50.

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